CN110114379A - Polymer composition for shrinkage packing film - Google Patents
Polymer composition for shrinkage packing film Download PDFInfo
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- CN110114379A CN110114379A CN201780079637.6A CN201780079637A CN110114379A CN 110114379 A CN110114379 A CN 110114379A CN 201780079637 A CN201780079637 A CN 201780079637A CN 110114379 A CN110114379 A CN 110114379A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
- B65B53/00—Shrinking wrappers, containers, or container covers during or after packaging
- B65B53/02—Shrinking wrappers, containers, or container covers during or after packaging by heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D75/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes, or webs of flexible sheet material, e.g. in folded wrappers
- B65D75/002—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes, or webs of flexible sheet material, e.g. in folded wrappers in shrink films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/023—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type using a coupling agent
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/044—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes using a coupling agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/046—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
- C08L2203/162—Applications used for films sealable films
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/32—Properties characterising the ingredient of the composition containing low molecular weight liquid component
- C08L2207/322—Liquid component is processing oil
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Abstract
Polymer composition comprising styrene butadiene block copolymer (SBC), can be used for shrink wrap.The polymer composition contains rigid star SBC block copolymer A, and for tool there are two short-chain branch, structure is single copolymer block (B/S)AiWith two long-chain branch, structure St‑[(B/S)A]n‑(B/S)AiOr [(B/S)A]n‑(B/S)Ai, and it is related to the production of shrinkage packing film and plural layers.
Description
Invention description
The present invention relates to the combination of polymers comprising the styrene butadiene block copolymer (SBC) for shrink wrap
Object, SBC block copolymer and the polymer composition for forming the polymer composition are used to prepare shrink pack
Fill the purposes of film and multilayer film.
EP-A 436 225 discloses a kind of purposes of styrene-butadiene block copolymer as heat-shrinkable film.Institute
It is straight chain or star-shaped for stating block copolymer, and also comprising mainly by conjugated diene group in addition to vinyl aromatic polymer blocks
At polymer blocks B.Film stretching is fixed on to more than 500%, and after cooling to room temperature by being heated to 60 to 100 DEG C
Tensional state.After printed patterns, these films can be processed into pod-like, and can be placed on bottle and in 70-
It bounces back again in 90 DEG C of the passage of heat, so that film is adhered on bottle.
Shrinkable film refer to can be contracted in a heated condition with the much the same film of its original dimension, and have simultaneously
High storage stability, that is to say, that they 20-40 DEG C at a temperature of be not in shrink.Furthermore they will not only have height
Transparency will also have high rigidity and high intensity.
EP-A 852240 describes linear styrene-butadiene's block copolymer and its mixture, takes under heat condition
Backward, the spontaneous contractility at 30 DEG C reduces.It is preferred that the structure of SBC is A-B-B, wherein A is the poly- of vi-ny l aromatic monomers
Object chain is closed, and B is the random copolymer chain of vi-ny l aromatic monomers and conjugated diene.Weight ratio S/B is 60:40 to 90:10.
US 7,037,980 describes total with irregular phenylethylene-butadiene block star butadiene-styrene block
Polymers；When compared with the pure styrene block with identical molecular weight, it shows reduced glass transition temperature, therefore improves
It is exposed to Shrinkage behavior when high temperature.The block copolymer also includes conjugated diene block B (structure is (B/S)-B-CA),
Or the block copolymer of especially structure (B/S) 1- (B/S) 2- (B/S) 3- (B/S) 4- (B/S) 5-CA, wherein (B/S) is nothing
Advise monovinylarene/conjugated diene block；CA is the coupling agent remnants of defeated troops；(B/S) 1 respectively has about 2.5 weight % with (B/S) 2
To the conjugated diene content of about 10 weight %；(B/S) 3, (B/S) 4, and (B/S) 5 respectively have about 30 weight % to about 70 weights
Measure the conjugated diene content of %.
WO2012/055919 describes star elastomer SBC block copolymer and its mixing at least two dissimilar arm
Object, wherein at least one arm include that soft aromatic vinyl/diene of pure ethylene base aromatics hard block S and the Tg temperature lower than 0 DEG C is poly-
It closes object block (B/S).Preferably there is the star of 3 or 4 arms, two of them S1- (B/S)-S2 arm is hard embedding with one or two
Section polymer S, has been bonded.The elastomer SBC block copolymer can be used for various applications, especially be used for foil.
US 2008/0269414 and US 2011/098401 describes the mixed of styrene-butadiene block copolymer A and B
Object is closed, can be processed to obtain having high convergency ability and high rigidity/high intensity heat-shrinkable film.Preferred SBC copolymerization
Object A is that linearly, structure is S- (B/S)A- S or such as single copolymer block (B/S)A, wherein (B/S)AIt is random copolymerization
Object hard block is made of the vi-ny l aromatic monomers of 65 to 95 weight % and the diene of 5 to 35 weight %；S is aromatic vinyl
Polymer hard block, molal weight Mw are 50000 to 500000g/mol.Preferably, SBC block copolymer B is star, tool
There is block of random copolymer (B/S)B, the two of the vi-ny l aromatic monomers of each 20 to 60 weight % of freedom and 80 to 40 weight %
End the hard block S1 and S2 of alkene and at least two different molecular weights form (US 2008/0269414).Alternatively, SBC block
Copolymer B is preferably star, and having structure is Se-(B/S)BOr Se-(B/S)B-SsShort-chain branch and structure be (B/S)A-Si-
(B/S)BOr (B/S)A-Si-(B/S)B-SsLong-chain branch, the short-chain branch and long-chain branch pass through magma (B/S)BOr (B/S)B-Ss
It links (US2011/098401A1), wherein Se, SiIt is long vinyl aromatic polymer blocks；SsIt is short vinyl aromatic (co) adoption
Close object block.If the content of white oil is 1.5-3.5% (weight) in mixture, particularly preferred shrinkage can get.
Still needed according to the shrink wrap of prior art production and is carried out in terms of natural shrinking, rigidity and toughness
It improves.
Therefore, it is an object of the present invention to provide a kind of polymer compositions based on SBC to be used for shrinkage packing film,
It has reduced natural shrinking rate and has enough ultimate shrinkages, higher rigidity and foot in greater than about 90 DEG C of temperature
Enough toughness.It is a further object to provide the hard block copolymers based on SBC, have in production equipment and increase
The lithium salts deposit of the space-time yield and reduction that add is formed, and can be used for producing the polymer group based on SBC of shrink wrap
Close object.
It is an object of the invention to a kind of star block copolymer A, include
Two short-chain branch, respectively single copolymer block (B/S)AiComposition, by 65 to 95 weight % aromatic vinyls
Monomer and the preparation of 35 to 5 weight % diene, glass transition temperature Tg A are 40 to 90 DEG C, and
Two long-chain branch, structure St-[(B/S)A]n-(B/S)AiOr [(B/S)A]n-(B/S)Ai, the two pass through interior block
(B/S)AiIt connects (being interconnected with one another by coupling agent), wherein block StBy the aromatic vinyl list of 95 to 100 weight %
The diene of body and 0 to 5 weight % composition；Block [(B/S)A]nBy one or more similar and different copolymer blocks (B/S)A
Composition, (B/S)AThe vi-ny l aromatic monomers of each 65 to 95 weight % of freedom and the diene composition of 35 to 5 weight %, and vitrifying
Transition temperature TgA is 40-90 DEG C；N is at least 1 natural number, preferably n=2 to 10, more preferable n=2 or 3, most preferably n=
2, and block (B/S)AiAs defined above, wherein
Block (B/S)AiMumber average molar mass MnIt is 5000 to 15000g/mol, entire block [(B/S)A]nNumber rub
That mass MnIt is 50000 to 150000g/mol.
In the context of the present invention, average molar mass Mn(size is measured according to ISO 16014-3:2012 by GPC
It excludes to be low T < 60 DEG C, and uses the relative calibration method based on polystyrene standard)." Wt.-% " or " weight % ratio " is indicated
Weight percent.
In the context of the present invention, " diene " refers to conjugated diene.Butadiene refers to 1,3- butadiene.
In the context of the present invention, glass transition temperature (Tg) is based on DIN EN ISO 11357-2 by DSC:
2014-07 measurement is evaluating the second heat cycles after 180 DEG C of rapid coolings with the 20K/ minutes rates of heat addition.
Block copolymer A
Preferably, copolymer block (B/S)AiMumber average molar mass MnIn the range of 6000 to 12000g/mol.
Preferably, entire block [(B/S)A]nMumber average molar mass MnIn the range of 60000 to 130000g/mol,
More preferable 70000 to 120000g/mol, most preferably 70000 to 100000g/mol.
Preferably, block StMumber average molar mass MnIt is 3000 to 8000g/mol.
Block [(B/S)A]nBy n similar and different copolymer blocks (B/S)AComposition, n is one or more, and preferably 2
To 10, more preferable 2 or 3, most preferably two, wherein block (B/S)AMolal weight and/or vinyl-arene/alkadienes
Ratio can be different.
Preferably, block [(B/S)A]nWith structure (B/S)A1-(B/S)A2-(B/S)A3Or it is preferred (B/S)A1-(B/
S)A2.In the structure, vinyl aromatic compounds/alkadienes ratio can be different in each B block/S.Therefore, long point
Branch preferably has structure St-(B/S)A1-(B/S)A2-(B/S)A3-(B/S)AiOr (B/S)A1-(B/S)A2-(B/S)A3-(B/S)Ai
Or it is preferred (B/S)A1-(B/S)A2-(B/S)AiOr especially preferred St-(B/S)A1-(B/S)A2-(B/S)Ai。
According to an embodiment, outer block (B/S)A1With than block (B/S)A2Higher mumber average molar mass Mn.Root
According to the embodiment, block (B/S)A1Mumber average molar mass MnIt is preferred that in the range of 30000 to 80000g/mol, and it is embedding
Section (B/S)A2Mumber average molar mass MnIt is preferred that in the range of 20000 to 50000g/mol.
Preferably, copolymer block (B/S)A(B/S)AiIndependently of one another by the aromatic vinyl of 85 to 93 weight %
The diene of monomer (especially styrene is made) and 7 to 15 weight % composition.The preferred isoprene of the diene or butadiene, it is special
Not preferred butadiene.
Copolymer block (B/S)A(B/S)AiGlass transition temperature be preferably 50 to 80 DEG C, particularly preferred 60 to 75
℃。
Specially suitable Hard block copolymers A is made of vi-ny l aromatic monomers and diene, vinyl aromatic monomer
(especially styrene) is 86 to 94 weight %, preferably 88 to 92 weight %, and diene (especially butadiene) is 6 to 14 weights
Measure %, preferably 8 to 12 weight %.The weight % is based on the weight of entire block copolymer.
Preferred block copolymer A includes (or being made from it) copolymer block (B/S)Aand(B/S)Ai, by vinyl
The polymer of the random distribution of aromatic monomer and diene forms.These can for example by randomizer (such as tetrahydrofuran or
Sylvite) in the presence of carry out anionic polymerisation using alkyl lithium compounds and obtain.It is preferable to use sylvite, wherein anionic initiator
Molar ratio with sylvite is 25:1 to 60:1, particularly preferred 30:1 to 40:1.This method can be realized simultaneously low ratio 1,2 and connect
Butadiene unit.Suitable sylvite is K alcoholates, is especially soluble in those of polymer solvent, for example, tert-pentyl alcohol compound or
Triethylammonium hydrogencarbonate salt or other tertiary alcohol compounds rich in C.
Based on all 1,2 connections, the summation of Isosorbide-5-Nitrae-cis- connection and the trans- connection of Isosorbide-5-Nitrae-, the 1 of butadiene unit, 2 connections
Ratio be preferably 8-15%.
It is particularly preferred that star block copolymer A has following (pseudo- linear) structure:
Wherein St,(B/S)A1,(B/S)A2, and (B/S)AiAs hereinbefore defined, X is coupling center, it be by active yin from
The sub- polymer end of the chain reacted with multifunctional coupling agent to be formed (i.e. by block (B/S)AiConnection).The multifunctional coupling agent is logical
It often can be any suitable polyfunctional compound, be preferably selected from epoxidized vegetable oil, especially epoxidized linseed oil or ring
Aoxidize soybean oil.
In the case where anion prepares polymer, molecular weight can be controlled by the ratio of amount of monomer and amount of initiator.
However, it is also possible to which initiator is repeatedly added after monomer feed generation, bimodal or multi-modal is as a result generated.Molecular weight is usually logical
Gel permeation chromatography (GPC) measurement in THF (as solvent) is crossed, uses polystyrene as standard.In anionic polymerisation
In the case where, weight average molecular weight is roughly the same with number-average molecular weight.
Star block copolymer A of the invention, which usually passes through cathode and is aggregated in nonpolar solvent, to be prepared, wherein usually making
Initiator is organo-metallic compound.Preparation method of the invention needs to add at least one coupling agent, usually poly-
It is added at the end of closing reaction, and at least one initiator described in a part is added when polymerization reaction starts, and initiator
Remainder is then then being added.
Method of the invention can prepare specific block copolymer A of the invention, with special star-shaped molecule structure,
There are two identical short branch and two identical long branches for tool.
Suitable initiator is organo-metallic compound in anionic polymerisation, and preferred as alkali compound is especially excellent
Select lithium compound.The example of initiator is lithium methide, ethyl-lithium, propyl lithium, n-BuLi, s-butyl lithium and tert-butyl lithium.Have
Usually (being dissolved in chemical inertness hydrocarbon) is added as a solution in machine metallic compound.The amount of addition depends on required in principle
Polymer molal weight, but usually 0.002-5mol% (being based on monomer molar amount).
Total amount used in above-mentioned initiator, as described above, with the addition of at least two batches.Solvent for use is preferably aliphatic hydrocarbon, example
Such as hexamethylene or hexahydrotoluene.
Anionic polymerisation usually also uses polar co-solvent (as randomizer), here, relative to initiator
Metal cation, cosolvent can see lewis base as.Preferred lewis base is aprotic, polar chemical combination object, such as ether and uncle
Amine.The example of particularly effective ether is tetrahydrofuran and aliphatic polyether, such as glycol dimethyl ether and diethylene glycol dimethyl ether.Uncle
The example of amine is triethylamine, tri-n-butylamine and pyridine.The amount for the polar co-solvent being added in nonpolar solvent is, for example, 0.5-5%
(volume).The particularly preferably tetrahydrofuran of 0.1 to 0.6 volume %.In many cases, amount very particularly preferably is
0.2 to 0.4 volume %.
The additional amount of lewis base determines the ratio that copolymerization parameter is connected with the 1,2- of diene units with 1,4- with its structure
Example.Based on all diene units, gained rubbery block copolymers usually have 20 to 80% 1,2- connection and 80 to 20%
1,4- connection.
Preferably, soluble potassium salt (as randomizer) is added to be used to replace cosolvent, especially potassium alcoholate.Here it is considered that
Sylvite with lithium-carbanion pair metal exchange by interacting, to form potassium-carbanion compound, preferentially with
Vi-ny l aromatic monomers (particularly preferred styrene) form adduct, and lithium-carbanion compound is preferentially (especially excellent with diene
Select butadiene) form adduct.Since potassium-carbanion compound is with high reactivity very much, even sub-fraction, i.e., 1/
10 to 1/50 amount is also enough together with main lithium-carbanion compound, makes vi-ny l aromatic monomers (particularly preferred benzene
Ethylene) and diene (particularly preferred butadiene)
Average incorporation probability it is suitable.It is preferable to use sylvite, and wherein the molar ratio of anionic initiator and sylvite is 25:1
To 60:1, preferably 30:1 to 40:1.The mole of lithium particularly preferably selected/potassium ratio is 33-39, to realize vi-ny l aromatic monomers
(optimization styrene) is roughly the same with the incorporation of diene (preferably butadiene).
It is also believed that existing in the course of the polymerization process, between living chain and between living chain and the salt of dissolution frequent
Metal exchange, and same chain is in one case preferentially and vi-ny l aromatic monomers, and particularly preferred styrene forms adduction
Object, and in another case then preferentially and diene, particularly preferred butadiene forms adduct.Thus, for aromatic vinyl
Monomer and diene, gained copolymerization parameter are roughly the same.Suitable sylvite especially potassium alcoholate, is especially soluble in that of polymer solvent
A bit, such as the tertiary alcohol compound at least five carbon atoms, for example, tert-pentyl alcohol compound or triethylammonium hydrogencarbonate salt or other be rich in
The tertiary alcohol compound of C.
The example of typical correspondent alcohol is 3- ethyl -3- amylalcohol and 2,3- dimethyl -3- amylalcohol.Tetrahydrolinalool (3,7-
Dimethyl -3- octanol) and 2- methyl -2- butanol (tert-pentyl alcohol) be proved to be specially suitable.In principle, to alkyl metal cpd
Inert other sylvite, as alcoholization potassium, and be suitble to.It can be mentioned that example have dialkyl group potassium amide, be alkylated
Diaryl potassium amide, alkyl sulfide alkoxide and alkylated aryl mercaptides.The block copolymer A for using sylvite to produce as randomizer
Usually the 1,2- connection with 8-15% is connected with the 1,4- of 92-85% (based on all diene units).
Polymerization temperature is usually 0 to 100 DEG C, and preferably 30 to 90 DEG C, particularly preferred 50 to 90 DEG C.Polymerization reaction is usually more
It is carried out in a stage, wherein initiator is added using double initiation methods with more batches.For example, this method is to prepare hard block St
Start.A part of monomer is used as the initial charge in reactor, and by the way that a part of initiator initiated polymerization is added.For
Obtain the chain structure for the determination that can be calculated by the amount of monomer and the initiator of addition, it is proposed that before second comonomer addition,
Realize high conversion (being higher than 99%).Certainly, this is not required.
The sequence of monomer addition depends on selected block structure.Using batch processes (batch process)
In the case of, preferably use all or part of of solvent, such as hexamethylene as initial charge first, then using a certain amount of
Initiator (such as s-butyl lithium) is used as initial charge, it is described it is a certain amount of depend on required molal weight, in addition so-called drop
Quantitative (for removing the trace impurity in solvent and tank).Then it is preferably added sylvite, such as tert-pentyl alcohol potassium, is preferably dissolved in
In hexamethylene, or complexing solvent such as THF be added in reactor, then-with end-blocks StLong branch feelings
Under condition-vi-ny l aromatic monomers of the first amount are added to form block St.Diene and vi-ny l aromatic monomers are then added, preferably
The two is added simultaneously.
Addition can divide multiple batches of progress, be optionally added together with other solvent, for example, for improve thermal diffusivity and
The solvent that component needed for maintaining is constituted.Block (B/S)A1Random structure and composition can be by diene relative to vinyl aromatic (co)
The quantitative ratio of compounds of group, the concentration (if using sylvite) of sylvite and the concentration of lewis base (if using lewis base)
It is determined with chemical structure and temperature.
Then, by the way that diene and vi-ny l aromatic monomers are added, by other block (B/S)A2,(B/S)A3Etc. being aggregated to
On the polymer chain of growth.Preferably, only by block (B/S)A2It is aggregated on the polymer chain of growth.Then be added diene and
Second of elicitation procedure is carried out before vi-ny l aromatic monomers, i.e. second of addition initiator, the diene and aromatic vinyl
Monomer is used for block (B/S)AiIt is aggregated on the polymer chain of growth.
In the case where carrying out double cause in same reactor, polymer (the i.e. block (B/S) that newly causesAi) and be aggregated in
Block (B/S) on the polymer chain of growthAiMolal weight it is actually identical.
According to the method for the present invention, after diene and vi-ny l aromatic monomers are added in last time, using coupling agent into
Row coupling, multiple polymer blocks (B/S)AiTherefore it bonds together, and then forms the block of the present invention with star-shaped molecule structure
Copolymer A.
Any polyfunctional compound usually can be used as coupling agent.Preferred coupling agent is selected from epoxidized vegetable oil,
Such as epoxidized linseed oil or epoxidised soybean oil, silane, such as alkoxy silane (such as Si (OMe)4), chlorosilane is (such as
SiCl4), Si (alkyl)2Cl2, Si (alkyl) Cl3, wherein alkyl is C1-C4Moieties (preferably methyl), the halogenation of aliphatic hydrocarbon
Object, such as methylene bromide or dichlorotoleune, tin tetrachloride, multifunctional aldehyde, such as terephthalaldehyde, multifunctional ketone, multifunctional ester, such as
Carboxylate, such as ethyl acetate, diethyl succinate, dimethyl adipate or diethylene adipate, multifunctional acid anhydrides, oligomeric epoxy
Compound such as 1,4-butanediol glycidol ether activates alkadienes such as di isopropenylbenzene, divinylbenzene or diphenylethyllene benzene；
Preferred coupling agent is epoxidized vegetable oil, such as epoxidized linseed oil or epoxidised soybean oil.
Coupling agent forms coupling centers X, passes through one of living anionic chain end and above-mentioned coupling agent and reacts formation.
The amount of coupling agent is calculated according to its degree of functionality and the amount of initiator used.Preferably, the coupling agent being added
Amount needs to be reacted with all living chains, this corresponds to the amount of active initiator (total amount of initiator subtracts titer).
In the case where ester group, it is necessary to consider that it forms the fact that two living chains, and on the contrary, for epoxides, alkyl halide and
Silane, each functional group form a chain living.For example, epoxidised soybean oil includes the fat being esterified as a triglyceride
Acid mainly has one or two epoxy group.Correspondingly, key is formed with three or four polymer chains, released sweet
Oil metal alcoholate because carboxyl also with other two chain bonding.
It is total to prepare block of the invention that identical initiator can be used in each initiation step of the method for the present invention
Polymers.But, however, it is also possible to use different initiators.
Polymer concentration can have large-scale selection, but preferred concentration should make the polymerization reaction knot of each block
Temperature when beam is no more than 100 DEG C, or if it exceeds the temperature, also can only be the short time to be more than, to avoid any bright
Aobvious too early heat terminates (premature thermal termination).Using batch charging in a stirring kettle method when,
Typical polymer concentration is 10-50% (weight), preferably 20-40% (weight), particularly preferred 25-35% after coupling method
(weight).
Other kinds of reactor also can be used in principle, do not have to stirring, and preferably share with reflux condenser,
In preferably reduce the internal pressure of reaction kettle with by boiling and reflux solvent come cooled reaction solution, for example, and cooling end
The annular reactor for dividing (such as heat exchanger) to be applied in combination.Or the combination using stirred tank and external heat exchanger.It can also
Block copolymer A of the invention is produced not have to the method (batch process) of batch charging, and uses continuation method
(continuous process) production.Latter method can be for example, by the various serial arrangements of above-mentioned reactor, or adopt
With in the tubular reactor with preferred static mixing elements, or using the group of tubular reactor and reactor listed above
It closes.Preferably, the quantity of reaction zone is equal to different monomers addition number+1 (addition of a coupling agent).
When starting and in reasonable time point, initiator system is mixed.Initiator system generally comprise initiator and
Randomizer and optional other solvents.Here preferably will solvent be added monomer feed in, make monomer reach reactor it
Preceding is in dilute form.
In a preferred embodiment, polymer concentration is held constant at 15 to 35 in reactor differential responses Duan Jun
In the range of weight %.In another preferred embodiment, after final monomer is added, polymer concentration is increased to
36-50 weight %.
Therefore, method of the invention has following characteristics:
A) double starting,
B) coupling step carries out (i.e. n+1 times) after feeding and polymerizeing for the last time, it is preferable that last time adds
Material and polymerization are the addition and polymerization of third time vi-ny l aromatic monomers and diene, and
C) secondary initiation carries out before last time feeds and polymerize, it is preferable that last time charging and polymerization are
The addition and polymerization of third time vi-ny l aromatic monomers and diene.
First causes the molar ratio (causing ratio) caused with second also works in the method for the invention, can influence this hair
The structure of bright block copolymer.In tool there are four in the case where the radial copolymer of arm, it is preferred cause than in 1.10:1 and
Between 2.50:1.In this way, a final vi-ny l aromatic monomers and diene are added after secondary initiation can produce on average
Two S being bondedt-(B/S)A1-(B/S)A2-(B/S)AiBranch and two (B/S)AiBranch (pseudo- linear configuration,
pseudolinear architecture)。
The initiation of double initiations is usually 10:1 to 1:10, preferably 4:1 to 1:4 than (initiation ratio), especially
Preferably 1:1 to 2.5:1.
The further work-up of block copolymer of the invention carries out by conventional method.It is recommended here that being grasped in stirred tank
Make, after coupling process, optionally using a small amount of alcohol (such as isopropanol) protonate possible a small amount of residual carbanion with
With the alcoholates (it may be generated in coupling step) of polymer-bound, to avoid in tank formed deposit and product change
Color, and reduce the viscosity of solution.Before further work-up, CO is used in a usual manner2/ water is acidified product slightly, in this way
The product then obtained be it is vitreous, without tone.It can choose with free radical scavenger or preferably clear with free radical
Except agent combination (such as C- free radical scavenger (such as alpha-tocopherol (vitamin E),GM and
GS) with the combination of O- free radical scavenger (such as Irganox 1010 and Irganox 1076) and with secondary oxidation inhibitor
(for example, the commercial product based on phosphite, such as three isononyl phenyl ester TNPP of phosphorous acid or168) combination) make
Polymer stabilizing, and solvent is removed using conventional method, it then squeezes out and is granulated.
A kind of preferred method for removing solvent is the concentration of reduction solvent stage by stage, wherein if between polymerization reaction use
It has a rest method, then advantageously solution is placed in the intermediate store in surge tank first, then preferably after through pump
Preferably higher than 100 to 140 DEG C of solvent boiling point of temperature is heated to (to hexamethylene by concatenated one or more heat exchangers
Speech is 180 to 220 DEG C), it is preferably 100-350m/s's by a vapor (steam) velocity then after through pressure holding valve
Short tube is transferred in pressure reduction vessel, is adjusted pressure and temperature, is preferably made solvent just start to condense, surface has one layer of solvent thin
Film is not dried；For hexamethylene (as solvent), preferably select here 100 to 140 DEG C temperature and 1.6 to 4.3 bars
Pressure.
It is preferred that pressure reduction vessel is discharged in solvent vapour upwards, post-processing is condensed and passes through, and concentration is the poly- of about 70-95%
Polymer solution forms laminar sediment in pressure reduction vessel substrate.Next heat is fed forward to from there through gear pump to hand over
It in parallel operation, then can be reheated, preferably to 170 to 230 DEG C.Then solution is depressurized again by pressure holding valve
To preferred double screw extruder, it is discharged in wherein solvent vapo(u)r by the ventilation dome of polymer feed point upstream and downstream.
Then the concentration of solvent is preferably further decreased in the extruder section with barrier screw element (its is sealed against one another), while true
Reciprocal of duty cycle continues to improve, and is preferably 1-30mbar squeezing out the upstream of head, and be preferably injected a small amount of water, until being reached
Solvent content preferably < 3000ppm, particularly preferably < 2000ppm.
In the end of extruder, melt can carry out strands granulation or granulation underwater, it is here preferred that granulation underwater work
Skill.However, it is also possible to remove solvent by other methods, such as the known film by optionally combining with extruder squeezes out
Machine (Filmtruder), or by steam stripping (steam stripping), these thermoplasticity for most of styrene-baseds
It is conventional method for elastomer.These methods can produce polymer flake.Particle or thin slice obtained, as other kinds of rubber
Glue is the same, and antiblocking agent, which can be used, to be prevented from adhering to.The example of antiblocking agent has
And/or tricalcium phosphate.
One of the method for the present invention is special to be characterized in that block copolymer A of the invention can be raw with good space-time yield
It produces.The space-time yield (STY) of batch polymerization process (batch polymerization process), i.e., from the first monomer addition
It (is that the addition of optional alcohol and reactor are arranged at this time at the time of coupling process terminates at the time of combination with the charging of the first initiator
At the time of being spaced apart the beginning) between time span, usually 0.5 to 3 hour, preferably 1 to 2.5 hour.
Block copolymer A according to the present invention is rigid compound, can be preferably used as preparing shrinkable film.
Another theme of the invention is comprising (or being made from it) component (a), (b), (c) and the combination of polymers of (d)
Object:
A) the component a) of 45 to 100 weight % is made up of:
A1 at least one of) 20 to 80 weight %, preferably 30 to 65 weight % star block copolymer A as defined above,
With
A2) 80 to 20 weight %, preferably at least one star block copolymer B of 70 to 35 weight %, (substantially)
It includes
Multiple short branches, structure Se-(B/S)BAnd at least one (preferably one) long branch, structure are (B/
S)Ae-Si-(B/S)B, wherein length branch is by coupling agent each other with block (B/S)BConnection, or
Multiple short branches, structure Se-(B/S)B-SsWith at least one (preferably one) long branch, structure is (B/
S)Ae-Si-(B/S)B-Ss；Wherein length branch is by coupling agent each other with block SsConnection；
Wherein polymer blocks SeAnd SiIt is identical；(hard) polymer blocks Se, SiAnd SsBy the second of 95 to 100 weight %
The diene of alkenyl aromatic monomer and 0 to 5 weight % are made；Copolymer block (B/S) Ae by 65 to 95 weight % vinyl aromatic (co)
The diene of race's monomer and 35 to 5 weight % are made, and glass transition temperature Tg A is 40 to 90 DEG C；Copolymer block (B/S) B
The vi-ny l aromatic monomers of each 20 to 60 weight % of freedom and the diene of 80 to 40 weight % are made, glass transition temperature
TgB is -80 DEG C to 0 DEG C；
B) at least one other thermoplastic polymer TP in addition to block copolymer A and B of 0 to 55 weight %；
C) at least one plasticizer of 0 to 0.8 weight %；With
D) at least one of 0 to 3 weight % is different from other additives or processing aid c)；
Wherein, component (a) and (b), (c) and the total amount of (d) is 100% (weight), and glass transition temperature Tg is by DSC root
Measured according to DIN EN ISO 11357-2:2014-07, evaluate from 180 DEG C be quickly cooled down after with the of the heating speed of 20K/min
2 heat cycles.Weight % indicates weight percent.In one embodiment of the invention, composition of the invention includes
Component (a) and (b), but component (c) and (d) also containing a small amount of (at least 0.1 weight %).
In the present invention, " diene " refers to conjugated diene.
Glass transition temperature Tg, especially TgAAnd TgB, by based on DIN EN ISO 11357-2:2014-07's
DSC measurement, evaluation is after 180 DEG C of rapid coolings with the 2nd heat cycles of the heating speed of 20K/min.
In polymer composition according to the present invention, the amount of component c) is preferably 0.10 to 0.80 weight %, more preferably
For 0.15 to 0.70 weight %, most preferably 0.20 to 0.60 weight %, especially 0.20 to 0.50 weight %.
Preferably, polymer composition of the invention includes (or composed of the following components) component:
A) 45 to 99.90 weight %,
B) 0.10 to 0.80 weight %
C) 0 to 54.90 weight %
D) 0 to 3 weight %.
It is highly preferred that polymer composition of the invention includes (or composed of the following components) component:
A) 45 to 99.85 weight %,
B) 0.15 to 0.70 weight %
C) 0 to 54.85wt.-%
D) 0 to 3 weight %.
In a preferred embodiment, polymer composition of the invention includes (or composed of the following components) group
Point:
A) 45 to 99.8 weight %,
B) 0.20 to 0.60 weight %
C) 0 to 54.8 weight %
D) 0 to 3 weight %.
If in polymer composition of the invention, there are optional components (b), (c) or (d), then respective minimum content
Usually 0.05 weight %.
Component (a)
Preferably, component a) is by a1) and a2) form, wherein a1) it is at least one (preferably a kind of) block copolymer A,
Content is 30 to 60 weight %, more preferable 33 to 50 weight %, most preferably 35 to 45 weight %；It a2) is at least one (preferably one
Kind) block copolymer B its content be 70 to 40 weight %, more preferable 67 to 50 weight %, most preferably 65 to 55 weight %.Base
In (a), a1) and total amount a2) be 100 weight %.
Block copolymer B
The mumber average molar mass Mn of the rigid polymer block Se or Si of block copolymer B are usually 5000 to 30000g/
mol.Block appears in end (Se) or at copolymer block (B/S)A(B/S)BBetween (Si).Short Si block with as soft phase
Copolymer block (B/S)BIncompatibility maximize.This means that the interphase formed between hard phase and soft phase in solids
It can be with very little.The weight ratio of phase, the phase very little that (10 to 40 DEG C) can soften within the scope of room temperature.Molecular weight usually passes through gel
Permeation chromatography (GPC) measurement in THF (as solvent), uses polystyrene as standard.
Star block copolymer B is prepared by using the sequential anionic polymerization method of double initiations.
Polymer blocks Se and Si composition having the same and mumber average molar mass Mn。
Block SsIt can have and block SeAnd SiIdentical composition, but its mumber average molar mass MnUsually less than 2500g/
mol。
Copolymer block (B/S)AeMumber average molar mass Mn be usually 30000 to 100000g/mol, preferably 40000
To 90000g/mol, more preferably 50000 to 80000g/mol.Copolymer block (B/S)AeComposition and attribute correspond to it is above-mentioned
Copolymer block described in block copolymer A (B/S)AComposition and attribute.
The mumber average molar mass Mn of copolymer block (B/S) B is usually 5000-40000g/mol；Preferably 7000 to
30000g/mol, more preferably 9000 to 25000g/mol.
Copolymer block (B/S) of the polymerized unit of vi-ny l aromatic monomers and diene in block copolymer BB(B/S)A
In distribution preferably it is random.These can for example by the presence of randomizer use alkyl lithium compounds carry out yin from
Son polymerize and obtains, the randomizer such as tetrahydrofuran or sylvite, is directed to block copolymer block (B/S) as described aboveAWith
(B/S)AiAs described.
Preferably, it is S that star block copolymer B, which averagely has there are three structure,e-(B/S)BShort-chain branch and a structure be
(B/S)Ae-Si-(B/S)BLong-chain branch, the two by coupling agent with block (B/S)BIt links each other, or there are three structures for average tool
For Se-(B/S)B-SsShort-chain branch and structure be (B/S)Ae-Si-(B/S)B-SsLong-chain branch, the two by coupling agent with
Block SsIt links each other.
Preferably star block copolymer B, wherein all blocks (B/S)BOr (B/S)B-SsThe sum of (i.e. soft phase), is based on
Entire star block copolymer B is 30 to 37 weight %, preferably 32 to 36 weight %, more preferable 33 to 35 weight %.
According to the present invention, all blocks " (B/S)B" and all blocks " (B/S)B-Ss" (if be added before link
Short block Ss) constitute soft phase.It in the latter case, is normally the S of hard blocksIt is dissolved in soft segment " (B/S)B" in, because it
It is too short and cannot mutually separate, therefore become block " (B/S)B" a part of soft phase.
It is highly preferred that it is S that star block copolymer B, which averagely has there are three structure,e-(B/S)BShort-chain branch and a structure
For (B/S)Ae-Si-(B/S)BLong-chain branch, the two by coupling agent with block (B/S)BIt links each other, or
It is S that it, which has average three structures,e-(B/S)B-SsShort-chain branch and structure be (B/S)Ae-Si-(B/S)B-Ss
Long-chain branch, the two by coupling agent with block SsIt links each other；
One or more of them (hard) polymer blocks Se, SiAnd SsBy 95 to 100 weight % vi-ny l aromatic monomers and
The diene of 0 to 5 weight % is made, block SeAnd SiWith mumber average molar mass MnFor 5000~30000g/mol, block SsNumber
Equal molal weight MnLower than 2500g/mol；
(hard) copolymer block (B/S)AeBy the vi-ny l aromatic monomers of 65 to 95 weight % and the diene of 35 to 5 weight %
It is made, glass transition temperature TgAIt is 40 to 90 DEG C, mumber average molar mass MnWithin the scope of 30000 to 100000g/mol, and
(soft) copolymer block (B/S)BThe vi-ny l aromatic monomers of each 20 to 60 weight % of freedom and the diene system of 80 to 40 weight %
At glass transition temperature TgBIt is -80 DEG C to 0 DEG C, mumber average molar mass MnFor 5000-40000g/mol.
Particularly preferably aforementioned star block copolymer B, wherein all blocks (B/S)BOr (B/S)B-Ss(i.e. soft phase)
Sum, be based on entire star block copolymer B, be 30 to 37 weight %, preferably 32 to 36 weight %, more preferable 33 to 35 weight
Measure %.
Specially suitable block copolymer B is based on entire block copolymer, by 60 to 80 weight %, preferably 67 to 73 weights
Measure the vi-ny l aromatic monomers (especially styrene) and 20 to 40 weight % of %, the preferably diene of 25 to 31 weight % (especially
It is butadiene) it is made.
Preferred block copolymer B is star block copolymer B, wherein introducing mumber average molar mass M before proceedingnIt is low
In the short polystyrene block S of 2500g/molsTo improve toughness/rigidity ratio.
The star block copolymer B. particularly preferably having following structure
Wherein Se, Si, Ss, (B/S)Ae(B/S)BAs hereinbefore defined, X is coupling centers, it is gathered by active anion
Close the object end of the chain reacted with multifunctional coupling agent to be formed (i.e. pass through block (B/S)BOr (B/S)B-SsLink).
Multifunctional coupling agent can be, for example, multifunctional aldehyde, ketone, ester, acid anhydrides or epoxides, especially epoxidation are sub-
Flaxseed oil or epoxidised soybean oil.
It is well known for preparing asymmetric star block copolymer by sequential anionic polymerization, and is particularly described in US
6,593,430 (the 1st rows of the 3rd column to the 45th row of the 4th column).
Block copolymer B is tough and tensile compound, is preferred for producing shrinkage packing film.
Plasticizer
(preferably a kind of) plasticizer (as component c)) optionally at least one in polymer composition of the invention is
The uniformly mixture of miscible oil or oil, especially mineral oil (or white oil) or dioctyl adipate.
Mineral oil or white oil refer to from the various colourless of mineral sources, especially petroleum distillate, tasteless, the advanced alkane of lightweight
Any one of hydrocarbon mixture.
, according to the invention it is preferred to which polymer composition includes plasticizer as component c).
Additive and/or processing aid
The additive and/or processing aid for the component d) being optionally present in polymer composition of the invention especially wrap
Include stabilizer, antiblocking agent, dyestuff and UV absorbent.It is preferable to use stabilizers, especially oxygen free radical scavenger, such as
Irganox 1010, Songnox 1010, Irganox 1076, Irganox 565 and its blend, carbon radicals scavenger,
Such as Sumilizer GS, Sumilizer GM and its blend and/or two-stage stabilising agent are such as168.The stabilization
Agent is commercially available.The dosage of above stabilizer is preferably 0.01-0.5% (weight), more preferable 0.1-0.3% (weight).Into
It is preferable to use antiblocking agents, such as high impact polystyrene (HIPS) for one step.The dosage of antiblocking agent is preferably 0.1 to 1 weight
Measure %.
Thermoplastic polymer
Polymer composition of the invention optionally includes 0 to 55 weight %, preferably 0 to 45 weight %, and more preferable 1 to 30
Weight %, most preferably the component b) of 5 to 20 weight %.Component b) be at least one in addition to block copolymer A and B (preferably
It is one or two kinds of) thermoplastic polymer.
As component b), specially suitable thermoplastic polymer is styrene polymer, such as standard polystyren
(GPPS), styrene-acrylonitrile copolymer (SAN), styrene-methylmethacrylate copolymer (S/MMA) or poly- methyl-prop
Olefin(e) acid ester, such as PMMA, polyester, such as polyethylene terephthalate (PET), polyolefin, such as polyethylene or polypropylene, or
Polyvinyl chloride (PVC) or those semi-crystalline materials.It is preferable to use be styrene polymer, especially GPPS.
Also polyacrylate, such as PnBA and other acrylic rubber, ethyl vinyl acetate polymer can be used
(EVA) etc..Thermoplastic polymer E can be mixed to improve rigidity, solvent resistance, impressionability, resistance to blocking, recyclable property
And adhesiveness.
Thermoplastic elastomer (TPE) (TPE) can also be used, such as linear or star in addition to a and b, hydrogenation or non-hydrogenated
Styrene-butadiene or styrene-isoprene block copolymer, example are double blocks and triblock copolymer.It is suitable this
Kind block copolymer can be commercially availableD,G orThermoplastic elastomer (TPE) is added usually may be used
Improve the toughness of Inventive polymers composition.
The method for preparing polymer composition
Another theme of the invention is the method for preparing polymer composition of the invention.Combination of polymers of the invention
Object can pass through any known method mixed component a) and optional components b), c) and d) obtain.However, it is preferable that by molten
Melt mixing blend components, such as joint squeezes out, mediates or preferred double screw extruder, more preferable counter rotating double screw squeeze out
Machine.For this method, a1 is can be used in component a)) and premix a2), or it is total using individually block as described above
Polymers A and B mix it according to the above method, then optionally addition b), c) and d) in any component and mixed.This
Usually at 160 DEG C to 300 DEG C, carried out at a temperature of preferably 180 DEG C to 250 DEG C, especially 200 to 220 DEG C.
Another theme of the invention is that polymer composition of the invention is preparing the purposes in film, especially for receiving
The purposes of contracting film.The preparation of shrink film is well-known.Known processing thermoplastic material (especially SBC) can be used
Method, can especially be squeezed out by thermoforming, be molded, roll, blow molding, compression moulding preferably given birth to by film extrusion
It produces.
Polymer composition of the invention is highly transparent, especially suitable for producing shrinkable film.
They have storage stability, and have low-down natural shrinking rate." natural shrinking " refers at 0 to 40 DEG C
In the range of store last from days to 3 weeks Spontaneous Contraction behavior.
Limit shrinkage degree is high, allows to be flexibly adapted to the package of processing conditions and high convex form." ultimate shrinkage "
(ultimate shrinkage) refers to stretches 550% (parallel with direction is squeezed out or opposite) of its initial length in film in advance
Afterwards, after impregnating 10 seconds in 90 DEG C of water-baths, squeezing out the parallel or opposite shrinking percentage in direction with film is 65% to 75%.
Compared with prior art, polymer composition of the invention shows higher rigidity, especially higher elasticity
Modulus and enough toughness.
Polymer composition of the invention, which is also particularly suitable, prepares multilayer film by coextrusion.Above-mentioned thermoplastic polymer
E is equally applicable to various layers.Mixture of the invention can use in the form of back sheet or in the form of outer layer herein.It is additional
Layer is used in particular for surface and is modified, and resistance to blocking energy improves hardness or change/reduction permeability.
The present invention is further illustrated by claim and following embodiment.
Analysis method
According to ISO 1133-1:2011, the melt mass flow that polymer melt is measured under 220 DEG C and 5kg load refers to
Number (i.e. MFI, [ml/10min]).
It by all solvents used and monomer drying and is purified using preceding.
Block copolymer A-C1 (comparative example (US2011/098401, block copolymer A))
In order to prepare linear styrene-butadiene block copolymer A-C1 (structure B/S), made using 2991ml hexamethylene
It is titrated to terminal (BuLi ic) for initial charge (ic) and with 1.6ml s-butyl lithium at 60 DEG C)；Then by 6.73ml 1.4M
Sec-Butyllithium solution (BuLi 1) is used as initiator, with 2.29ml 0.1175M tert-pentyl alcohol potassium (PTA) solution as randomizer
It is mixed, and mixture is cooled to 40 DEG C.Polymerization reaction is divided into two parts progress.For this purpose, every part is added simultaneously respectively
450g styrene (S1) and 50g butadiene (B1), and by inverse cold limitation maximum temperature at 75 DEG C.Then by the way that 0.72ml is added
Isopropanol terminate living polymer chains, be added CO2/ water is used for acidifying mixture, adds stabiliser solution.It is dried using vacuum
Case evaporating cyclohexane.
Block copolymer A includes the white oil of 5 weight %.
Ini=initiator；BuLi=s-butyl lithium
Every 100 weight parts monomers of phm=' ' (initiator, the weight % of the components such as coupling agent are the gross masses based on monomer
It calculates)
Block copolymer A-1
Star block copolymer A-1, structure are [St-(B/S)A1-(B/S)A2-(B/S)Ai]2X[(B/S)Ai]2, it is to pass through
(monomer S1 to S4) and butadiene be (sequential anionic polymerization of monomer B1 to B3) and subsequent epoxidised soybean oil for styrene
(referring to the table 1) for being coupled to prepare.Use 4785ml hexamethylene as initial charge (ic), 1.6ml sec-butyl is used at 160 DEG C
Lithium (BuLi ic) titrates to terminal, is cooled to 40 DEG C, and 6.73ml 1.4M Sec-Butyllithium solution (BuLi 1) is then added and is used for
Cause (Ini1) and 2.29ml 0.1175M tert-pentyl alcohol potassium (PTA) solution, as randomizer.Then, mixed initiator mixes
Mixture is simultaneously cooled to 40 DEG C by object.In the next step, 50 grams of styrene are added and carry out polymerization reaction to all monomers
It is consumed and (is reduced by the temperature of reaction mixture to identify).In the next step, while 55 grams of butadiene and 445 grams are added
Styrene, and polymerization reaction is made to carry out to all monomers being consumed and (being reduced by the temperature of reaction mixture to identify).
In the next step, while 25 grams of butadiene and 225 grams of styrene are added, and carries out polymerization reaction to all
Monomer is consumed and (is reduced by the temperature of reaction mixture to identify).Next, by the way that the second initiator is added into reaction
Mixture (Ini 2), i.e. addition 2.69ml 1.4M s-butyl lithium (BuLi 2) solution, are then added 0.917mL uncle 0.1175M
Amylalcohol potassium (PTA) solution (as randomizer), is stirred simultaneously.In the next step, while 20 grams of butadiene and 180 grams are added
Styrene, and polymerization reaction is made to carry out to all monomers being consumed and (being reduced by the temperature of reaction mixture to identify).
Finally, 1.88g is addedD82 (being dissolved in 10mL hexamethylene) is as coupling agent and it is made to react 10 points
Clock.Finally, using 0.5ml isopropanol termination mix and using CO2/ water acidification, and be added stabiliser solution (
1010)。
Analyze data: MFI=12ml/10min
Table 1: block copolymer A-1 (composition and order of addition)
Block copolymer B-C1, B-1 and B-2
(present invention is poly- by star block copolymer B-C1 (block copolymer B of=US2011/098401A1), B-1 and B-2
Block copolymer used in polymer composition) be prepared by the following method according to the data in table 2: sequential anionic polymerization and
Coupling agent (epoxidised soybean oil) then is added.Use the hexamethylene of 358wt% (phm) as initial charge (ic) and 1.6
At DEG C to terminal with 1.6ml s-butyl lithium (BuLi ic) titration, and 40 DEG C are cooled to before 0.506wt.- is added.For drawing
The 0.1175M tert-pentyl alcohol potassium (PTA) of the % (phm) and 0.1363wt% (phm) of the 1.4M Sec-Butyllithium solution (BuLi 1) of hair
Solution is as randomizer.In order to form copolymer block (B/S)AOr (B/S)Ae, styrene 1 (S1) described in table 2 is added
With the amount of butadiene 1 (B1).
After polymerization reaction, the initiator (Ini 2) of second group of amount is the 1.4M Zhong Ding of 0.866 weight % (phm)
Base lithium solution (BuLi 2), for causing the 0.1175M tert-pentyl alcohol potassium of second group of chain and 0.3066 addition as randomizer
(PTA) it the weight % (phm) of solution and is mixed into polymerization reaction.Then, styrene 2 and styrene 3 and butadiene 4 is added
Mixture (copolymer block (B/S) B) and styrene 4, and make its polymerization.Finally, being added 0.188 weight %'s (phm)
Solution of the Edenol D82 as coupling agent in hexamethylene, and it is whole using the isopropanol of excessive (total amount based on sec-BuLi)
Only mixture.
Finally, by mixture CO2/ water is acidified and uses Irganox 1010 solution-stabilized.
Analyze data: block copolymer B-C1, B-1 and the B-2 of MFI=12ml/10min
Table 2: the chemical composition of block copolymer B-C1, B-1 and B-2
The preparation of polymer composition
All blends (temperature is 200 to 220 DEG C) on counter rotating twin screW extruder produce and squeeze out 250 μ m-thicks
Film.
Then, film is cut into the band of at least 10cm long He 5cm wide, and is placed on the damping jaw of cupping machine
In, free clamping length is 5cm.At 80 DEG C, band is stretched strain, direction and extrusion direction phase in cupping machine
Instead, the elongation strain factor is 5.5 (stretching factor), and is quickly cooled to 23 DEG C in a stretched state.
It is on oriented film and parallel with direction is squeezed out according to ISO 527-1:2012, determine all mechanical datas, i.e. poplar
Family name's modulus and fracture strength.
For measuring contraction data, i.e. natural shrinking and ultimate contraction (natural shrinkage and ultimate
Shrinkage), the width of stretch band is reduced to one third or they is cut into the band that width is at least 1cm.Fillet is used
In the determining ultimate shrinkage value in 90 DEG C of water-bath after 10 seconds.In order to determine natural shrinking, by band thermostatically controlled 40
It is stored 4 days in DEG C water-bath.
Table 3 shows the embodiment of the present invention 1 and 2, comparative example 1 (according to the blend of US2011/098401A1) and comparison
The polymer composition of example 2 to 4 data obtained.As mineral oil, using from H&R's70 medical oil.
Table 3: the machinery and shrinkage of the oriented film of the present invention and comparative polymer composition
Wt.-%* (the php)=parts by weight based on 100kg polymers compositions A
Table 3 shows that polymer composition of the invention, especially mineral oil content are 0.5 weight %'s (Examples 1 and 2)
Those, especially suitable for producing shrinkable film.They are stable storings, and (especially embodiment 1) show it is minimum
Natural shrinking rate (value < 2.8% at 40 DEG C, storage time are 4 days).
Ultimate shrinkage degree at 90 DEG C is very high (> 70%), therefore allows to wrap up the shape of height protrusion.With existing skill
Art (such as comparative example 1) is compared, they show higher rigidity, and especially higher elasticity modulus (is parallel to and squeezes out direction
Value be greater than 950MPa), and also there is enough toughness (be parallel to squeeze out the smallest breaking strain in direction be greater than 250%).
On the contrary, the property of comparative example 1 to 4 is clearly worse (i.e. higher natural shrinking and/or lower breaking strain).
Claims (20)
1. a kind of star block copolymer A is included
Liang Geduan branch, each single copolymer block of freedom (B/S)AiComposition, (B/S)AiBy 65 to 95 weight % aromatic vinyls
Monomer and the preparation of 35 to 5 weight % diene, glass transition temperature TgAIt is 40 to 90 DEG C, and
Liang Gechang branch, structure St-[(B/S)A]n-(B/S)AiOr [(B/S)A]n-(B/S)Ai, the two pass through interior block (B/
S)AiIt connects, wherein block StBy the diene preparation of the vi-ny l aromatic monomers and 0 to 5 weight % of 95 to 100 weight %；Block
[(B/S)A]nBy one or more similar and different copolymer blocks (B/S)AComposition, each copolymer block by 65 to
The preparation of the diene of the vi-ny l aromatic monomers of 95 weight % and 35 to 5 weight % and glass transition temperature TgAIt is 40-90 DEG C；n
It is at least 1 natural number, preferably n=2 to 10, more preferable n=2 or 3, most preferably n=2, block (B/S)AiAs defined above,
Wherein block (B/S)AiMumber average molar mass MnIt is 5000 to 15000g/mol, entire block [(B/S)A]nEqual mole of matter of number
Measuring Mn is 50000 to 150000g/mol.
2. star block copolymer A according to claim 1, wherein the block StMumber average molar mass MnFor 3000 to
8000g/mol。
3. star block copolymer A according to claim 1 or 2, wherein copolymer block (B/S)A(B/S)AiBy what is polymerize
The vi-ny l aromatic monomers and diene of random distribution form.
4. star block copolymer A as claimed in one of claims 1-3, wherein block [(B/S)A]nIt is more excellent by 2 to 10
Select 2 or 3, most preferably 2, different copolymer block (B/S)AComposition, wherein different blocks (B/S)AMolal weight
And/or vinyl-arene/alkadienes ratio is different.
5. star block copolymer A as claimed in one of claims 1-4, wherein copolymer block (B/S)AiEqual mole of number
Mass MnIt is 6000 to 12000g/mol.
6. star block copolymer A as claimed in one of claims 1-5, wherein copolymer block (B/S)AAnd/or (B/
S)AiBy the diene of the vi-ny l aromatic monomers of 85 to 93 weight %, especially styrene and 7 to 15 weight %, especially isoamyl
Diene or butadiene, preparation.
7. according to claim 1 to any one of 6 star block copolymer A, structure are as follows:
Wherein St and (B/S)AiAs defined above, (B/S)A1(B/S)A2It is two different copolymer blocks as defined above
(B/S)A, X is coupling centers, is reacted with multifunctional coupling agent by active anionic polymerization object chain and is formed.
8. a kind of preparation method, is used to prepare star block copolymer A as claimed in one of claims 1-7, feature exists
In:
A) double starting,
B) coupling step carries out after last time addition and vinyl aromatic monomer and diene, and
C) secondary initiation carries out before last time addition and vinyl aromatic monomer and diene.
9. one kind includes component (a) and optional (b), (c) with the polymer composition of (d), include:
A) the component a) of 45 to 100 weight %, composed of the following components:
A1) be 20 to 80 weight %, preferably 35 to 65 weight % it is at least one according to claim 1 to any one of 7 star
Shape block copolymer A, and
It a2) is 80 to 20 weight %, preferably at least one star block copolymer B of 65 to 35 weight % has
Multiple structures are Se-(B/S)BShort branch and at least one, preferably one, structure be (B/S)Ae-Si-(B/S)BLength
Branch, the two pass through block (B/S)BConnection, or；
Multiple structures are Se-(B/S)B-SsShort branch and at least one, preferably one, structure be (B/S)Ae-Si-(B/S)B-Ss
Long branch, the two pass through block SsConnection；
Wherein polymer blocks SeAnd SiIt is identical；Polymer blocks Se, SiAnd SsBy the aromatic vinyl of 95 to 100 weight %
The diene of monomer and 0 to 5 weight % are made；Copolymer block (B/S)AeBy the vi-ny l aromatic monomers and 35 of 65 to 95 weight %
Diene to 5 weight % is made, glass transition temperature TgAIt is 40 to 90 DEG C；Copolymer block (B/S)BEach freedom 20 to 60
The diene of the vi-ny l aromatic monomers of weight % and 80 to 40 weight % are made, glass transition temperature TgBIt is -80 DEG C to 0
℃；
B) at least one other thermoplastic polymer in addition to block copolymer A and B of 0 to 55 weight %；
C) at least one plasticizer of 0 to 0.8 weight %；With
D) at least one of 0 to 3 weight % is different from other additives or processing aid c)；
Wherein component (a), (b), (c) and the summation of (d) is 100 weight %, and glass transition temperature Tg is by DSC according to DIN EN
ISO 11357-2:2014-07 measurement, evaluation are followed after 180 DEG C of rapid coolings with the 2nd heating of the rate of heat addition of 20K/min
Ring.
10. polymer composition according to claim 9, it includes 0.10 to 0.80 weight %, preferably 0.15 to 0.70 weight
Measure %, the component c) of more preferable 0.20 to 0.60 weight %.
11. polymer composition according to claim 9 or 10, the wherein copolymer block (B/S) of block copolymer BAeNumber
Equal molal weight MnIt is 30000 to 100000g/mol.
12. according to the polymer composition of any one of claim 9-11, wherein block SeAnd SiMumber average molar mass MnFor
5000 to 30000g/mol.
13. according to the polymer composition of any one of claim 9-12, wherein copolymer block (B/S)BEqual mole of matter of number
Measure MnIt is 5000 to 40000g/mol.
14. according to the polymer composition of any one of claim 9-13, wherein block SsMumber average molar mass MnIt is lower than
2500g/mol。
15. according to the polymer composition of any one of claim 9-14, wherein copolymer block (B/S)Ae(B/S)BBy
The vi-ny l aromatic monomers and diene of the random distribution of polymerization form.
16. according to the polymer composition of any one of claim 9-15, wherein all blocks in star block copolymer B
(B/S)BOr (B/S)B-SsSummation content, be based on entire star block copolymer B, be 30 to 37 weight %, preferably 32 to
36 weight %, more preferable 33 to 35 weight %.
17. wherein star block copolymer B has following knot according to the polymer composition of any one of claim 9-16
Structure:
Wherein Se, Si, Ss, (B/S)Ae(B/S)BAs defined above, X is coupling centers, passes through active anionic polymerization object chain
It reacts and is formed with multifunctional coupling agent in end.
18. a kind of method for being used to prepare the polymer composition according to any one of claim 9-17, including by means of mixed
It attaches together and sets, such as kneader or extruder, melting mixing component a) and optional components at being 160 DEG C to 300 DEG C in temperature range
B), c) and d).
19. a kind of purposes of the polymer composition according to any one of claim 9-17, is used to prepare film, especially shrinks
Film.
20. a kind of shrink film, by being prepared according to the polymer composition of any one of claim 9-17.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP16206594.0 | 2016-12-23 | ||
| EP16206594 | 2016-12-23 | ||
| PCT/EP2017/082761 WO2018114569A1 (en) | 2016-12-23 | 2017-12-14 | Polymer compositions for shrink-wrap films |
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| CN110114379A true CN110114379A (en) | 2019-08-09 |
| CN110114379B CN110114379B (en) | 2022-07-22 |
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| CN201780079637.6A Active CN110114379B (en) | 2016-12-23 | 2017-12-14 | Polymer composition for shrink wrap films |
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|---|---|
| US (1) | US11041070B2 (en) |
| EP (1) | EP3559064B1 (en) |
| JP (1) | JP7083349B2 (en) |
| KR (1) | KR102598454B1 (en) |
| CN (1) | CN110114379B (en) |
| ES (1) | ES2829099T3 (en) |
| MX (1) | MX2019006344A (en) |
| WO (1) | WO2018114569A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110536930A (en) * | 2017-02-21 | 2019-12-03 | 英力士苯领集团股份公司 | Internality is without viscous shrink sleeve material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118574889A (en) | 2021-09-10 | 2024-08-30 | 英力士苯领集团股份公司 | SBC polymer compositions with improved organoleptic properties and low film blocking properties |
| WO2023036918A1 (en) | 2021-09-10 | 2023-03-16 | Ineos Styrolution Group Gmbh | Organoleptically improved, low film-blocking styrene butadiene block copolymers |
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- 2017-12-14 CN CN201780079637.6A patent/CN110114379B/en active Active
- 2017-12-14 EP EP17816785.4A patent/EP3559064B1/en active Active
- 2017-12-14 MX MX2019006344A patent/MX2019006344A/en unknown
- 2017-12-14 KR KR1020197019771A patent/KR102598454B1/en active IP Right Grant
- 2017-12-14 ES ES17816785T patent/ES2829099T3/en active Active
- 2017-12-14 US US16/471,827 patent/US11041070B2/en active Active
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| DE10306891A1 (en) * | 2003-02-18 | 2004-08-26 | Basf Ag | Transparent vinyl-aromatic-diene block copolymers with star structure, used for molding, film, fibers or foam, e.g. coat hanger or packaging, has rigid blocks of different molecular weight and 2 types of random flexible blocks |
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Also Published As
| Publication number | Publication date |
|---|---|
| MX2019006344A (en) | 2019-11-07 |
| EP3559064B1 (en) | 2020-09-23 |
| JP7083349B2 (en) | 2022-06-10 |
| US20200095416A1 (en) | 2020-03-26 |
| ES2829099T3 (en) | 2021-05-28 |
| US11041070B2 (en) | 2021-06-22 |
| WO2018114569A1 (en) | 2018-06-28 |
| KR20190097108A (en) | 2019-08-20 |
| JP2020502352A (en) | 2020-01-23 |
| KR102598454B1 (en) | 2023-11-03 |
| CN110114379B (en) | 2022-07-22 |
| EP3559064A1 (en) | 2019-10-30 |
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